Highly condensed heterocyclically bound anthraquinone derivatives containing nitrogen and process of making same



Patented July 7, 1936 UNITED STATES mrs NET OFFICE HIGHLY CONDENSEDHETEROCYCLICALLY BOUND ANTHRAQUINONE DERIVATIVES CONTAINING NITROGEN ANDPROCESS OF MAKING SAME Wilhelm. Moser, Biehen, near Basel, and WalterFioronir Binningen; near Basel, Switzerland; assignors to firm ofSociety of Chemical In.- dust'ryin Ba'sle, Basel, Switzerland NoDrawing. Application February 25, 19.35," Seria-LNo'. 8,217.. InSwitzerland February 27,

6 Claims.

The present process relates to the manufacture of highly condensedheterocyclically bound anthraquinone derivatives containing nitrogenwhich are valuable vat-dyestufis.- It comprises the process of makingthese dyestufis, as well as the new products themselves.

It has been found that the compounds of the general formula 0 in which9: represents NHz Oran acidylaminogroup, and y a hydrogen atom or aClix-group, are valuable intermediate products for the manufacture ofnew vat-dyestuffs, which are themselves characterized by the atomicskeleton or after any of the condensation which effect the connection ofthe carbon atoms in the 9:9 and 8:8 positions.

The products in which the heterocyclic condensation is carriedout-merely between the carbon atoms 2 and 2 correspondto the generalformula r in which :1: stands for an NI-Iz-g-roup or anacidyla-minmgroup; and 1 stands for H. The heterocyclic ringclosureleads toproducts which belong to the" ZrT-dianthrimide-l:1'-carbazole'series and therefore correspond to the general formula in which 2 standsfor an NH-group. The condensation leading to; this ring closure isadvantageously carried out by treating the parent material withsalt-like condensation products,

.such as, for example aluminium chloride or aluminium bromide withaddition of sodium chloride or ferric chloride, or also with condensingagents having an alkaline action such as caustic alkali, mostadvantageously in the form of alcoholic;

caustic alkali; The dyestuffs of the dianthrimidecarbazole series aredark powders dissolving in I sulfuric acid with characteristicfluorescence, and

dyeing cotton from the vat olive tintsl 1 5 I If'the parent materials ofthe general Formula I or of the general Formula III are treated withsulfuric acid in the presence of suitable reducing agents,.preferablyfinely divided metals, such as, for example, very pure finely dividedcopper or 110 finely divided aluminium, condensation takes place betweenthe 9:9'-carbon atoms with formation of productsof the general formulain which a: stands'for an'NHz-group or an acidylamino-group, y for aCIR-group 'or'a hydrogen atom, and z for an NH-group or a CHN- group.The product of the general Formula V may also be obtained by causingsalt-like condensing agents or condensing agents having analkaline'action to react in the manner described with the'product of theFormula IV. The products, of thegeneralFormula V are therefore 2:2-

iminornesobenzdianthrones, or compounds of the phenantridine serieswhich may be described for example Y as allopyridinomesobenzdianthrones.

' They are valuable vat-dyestufis dissolving in sul- 7 furic acid to asolution having'a characteristic "brown tints. 7

Now, the products of the general Formulas IV and V are converted, byfurther treatment with sulfuric acid, in the presence of oxidizingagents;

suchas, for example manganese dioxide or biin the 8:8 positions, intonew compounds of the general formulas 2 stands for the coloration, anddyeing cotton fromthe vat red to chromate, by, direct linkage of thecarbon atoms in which ts, y'and 2 have the meaning indicated;

above. r

The products of the general Formula VII may also be obtained by treatingthe products of the general Formula VI in known manner with con-idensing agents which are salt-like or have'an alkaline action. Theproducts of the general (VII) Formula VII areimino-meso-naphthodianthrones V or allopyridino-meso-naphthodianthrones.They "also dissolve in sulfuric acid to a solution having acharacteristic coloration and a red fluorescence, and produce orange tobrown tints from thevat. 7

1 All the products of the general. Formulas III,

.V and. VII may be converted into vat-dyestuffs which are stillmorevaluable by treating them with halo-genating'agents, i. e. bychlorinating,

brominating or iodizing. Particularly valuable effects are obtained bychlorinating the dyestufis of the general Formula VII. Among the newproducts those are particularly valuable in which v The followingexamples illustrate the invention, without however limiting the same,the parts being by weight Example 1 Into a mixture of' parts ofaluminium ch10 ride and 20'parts of dry common salt, at 150. 0.,

there are introduced 5 parts of. 2-amin0-1:1-di 1 anthraquinonylof theformula halogenating agent a mixture; in'approximately 7 which as beobtained by treating with a de -r 7' molecular proportions, of al-halogen-Z-ac'yb' aminoanthraquinone and a l-halogenanthraquinone, andthen saponlfying the product thus obtained. The mixture is kept at atemperature of -160" C..for2 hours, and then 'poured upon ice.Concentrated hydrochloric acid is then added and the whole is boiled andfiltered and the solid matter washed withwaterluntil neutral.

This product, probably 2 :'2- dianthrmldb1 fl carbazole of the formulais a dark brown body, soluble in sulfuric acid to a brown-redfluorescing-solution. The vat is brown-red; it dyes cotton olive tints.

Example 2 obtained in this manner is purifiediby extraction with glacialacetic acid, when it becomes a brightbrown body, yielding .a greensolution in sulfuric acid. In the same manner '2-phthalimino-2-methyl-meso-benzdianthrone of the formula 'may be made from2-phthalimino- 2'-methyl- 1:1-dianthraquinonyl; also the '2z2-diphthal-"imino-mes04oenzdian-throne from the 2:2'-diph'thalimino-l 1'-dianthraquinonyl.

thus obtained forms dark red-brown crystals sol- 5 uibre finsulf-uricacid to :a, :pure :green solution. lllhetvat is :green; l

in like mannerthere isobta'ined the z-amino- 2':methylemeso-benzdianthrone 0f the tormu-la CHIK from the correspondingphthalimino-compound; this product dissolves in sultur-ic acid to a pureY green solution and yields a bluish-green vat. From the 2 2'-diphthalimino-meso-benzdianthrone there is obtained the2:2'-diamino-mesobenzdianthrone, which forms dark violet crystalssoluble in sulfuric acid to a pure bluish-green solution and yielding-abluish-green vat.

Example 4 Into amass of parts of potassium hydroxide and 120 partslay-"volume 'of'absolute alcohol 'lieatedto 14i) there are introduced at-150" 0., 20 parts of 2-amino-meso benzdianthrone (compare ExamplevB).Mter'rhour at -.-1'60 Cuthemass is mixedwith waterand worked up in theusual manner; The carbazoi'e thus ob- '60 tained which is apparently2:2-imino-mesobenzdianthrone of the formula is a; brown-red body whichdissolves in sulfuric acid to a, pure green solution and dyes cotton ina bluish-green vat red-brown tints.

phthalimino-meso-naphthodianthrone V In likemanner there is obtainedfrom 2-amino 2 methyl-meso-benzdianthrone (compare Example 3) aphenanthridina, namely the allopyridino-meso-benadianthrone of theformula 0 1;" 1 This is a brown-red body which dissolves in V sulfuricacid toa yellow-green solution and dyes cotton in a. reddish-bluervatsalmon red tints.

Example 5 'Into 500 parts of concentrated sulfuric acid there areintroduced at ordinary temperature 10 parts of2phthalimino-meso-benzdianthrone (compare Example 2) and then 10 partsof manganese dioxide, and the whole is'stirred for 2 hours 'at'theordinary temperature, drained on a stone, filtered and transferred toice. After boiling and filteringthe solid matter is washed.

with hotwater 'until neutral and dried. This 2- of the formula is abrown yellow body, soluble in sulfuric acid to a pure red,fiuorescingsolution.

From 2-phthalimino- 2-methyl-meso-benzdi- "anthro ne there maybeobtained the 2-phthal imino-Z' -methyl-meso-naphthodianthrone, ayellow body which dissolves in sulfuric acid to a redfluorescingisolution. Y 7 P The 2:2 -irninomesobenzdianthrone yields;un-

der similar conditions the 2:2:-1imino-meso naph thodianthrone of theformulav a'red-brown body which dissolves in sulfuric acid ,42.3 V to;alsolution whichfluoresces bluish-red. The.

vat is pure green.

When the 2'-phthalimino-meso naphthodi- 'anthrone or the2-phthalimino-2"-methy1-mesonaphthodianthrone is saponified by theprescription given in Example 3, there is obtained the corresponding2-amino-compounds which i dissolve to pure redfluorescing solutions insulfuric acid. 7 g r e The 2-amino-2'-methyl -'mes0 naphthodianthroneyields when condensed in accordance with theprescription of Example 4aphenanthridinederivative, the allo pyridino-meso-naphtho-die anthrone ofthe formula This is a brown body which dissolves in sulfuric acidto ablue-violet solution and dyes vegetable fibre in a violet vat 'fastorange tints.

" Example '6 Into 60 parts of nitrobenzene are introduced .5

parts of allo pyridino meso benzdianthr'one (made as described inExample 4). This suspension is heated to Crand into it areadded by drops15 parts of sulfuryl' chloride in the course of 2 hours, the temperaturebeing 115-120'8 C. After, cooling and filtering, the filtrate isdistilled with steam. The residue of the distilla-' tion, presumably atrichloro-derivative, is a dark red-brown, crystalline powder which dyescotton in a grey-blue vatBordeaux red tints and dis-.

solves in sulfuric acid to an olive-greensolution;

The bromination of this product in chlorosulfonic acid yields, whensufiicient bromine is used, a tribromo-derivative that dyes cottonredbrown. V

The product of the first paragraph-of this example, when oxidized by theprescription given in Example 5, yields atrichlorinatedalloy-pyridino-meso-naphthodianthrone 1 which is a brown body,dyeingcot-ton in a blue-black vati yellow brown tints. 'The' sulfuricacid solution is pure blue. P m

' i Example 7 'Into a mixture, at C of 100 parts of aluminium chlorideand 20 parts of dried common '(compare Example 3).

The mixture is maintained for 2 hours at 1501'60 C., then'transferred toice, whereupon concen-' trated hydrochloric acid is added, the whole isboiled and then filtered, and the solid matter washed neutral.

2:2' imino-meso-naphthodianthrone, is redbrown and dissolves in sulfuricacid to a solution which fiuoresces bluish-red. The vat is pure yellowgreen.

The product, apparently the salt, there are introduced'5 parts of2-amino- 6Q meso-benzdianthrone 50 0.; there are added 2 litres ofcaustic soda solution of 36 B. and 1 kilo of hydrosulfite conc. powderis strewn in, while stirring. After 10-15 minutes the dyestuff isvatted, the solution is added to a bath which contains 320 litres ofwater at 50 C., 0.4 litre of caustic soda solution of 36 B. and 0.1 kiloof hydrosulfite conc. powder. 20 kilos of Well wetted cotton are nowintroduced and dyeing is continued for hour at 40-50 C. After 10 minutesfurther dyeing, 40 litres of common salt solution (of 20 per cent.strength) are added. When dyeing is complete, the goods are wrung out,suspended in the air for oxidation, rinsed and soaped as usual.

What we claim is:

1. In the manufacture of highly condensed anthraquinone derivatives, thestep which consists in treating compounds of the general formula f1 Y IC@CH:

with aluminium chloride. 7

2. In the manufacture of highly condensed anthraquinone derivatives, thestep which consists in treating compounds of the general formula whichproducts are dark powders dissolving in sulfuric acid to olive-green topure blue solutions having a yellow-red fluorescence, and dyeing cottonfrom a grey-blue to blue-black hydrosulfite vat fast Bordeaux toyellow-brown tints.

4. Process for the manufacture of highly condensed heterocyclicallybound anthraquinone derivatives containing nitrogen, consisting incausing sulfuric acid in the presence of finely divided copper, andsulfuric acid in the presence of manganese dioxide and a chlorinatingagent to react consecutively with the products of the formula l A CH:

and treating the products, prior to one of the two last steps, withaluminium chloride.

5. The halogenated highly condensed heterocyclically bound anthraquinonederivative containing nitrogen which corresponds to the formula whichproduct is a dark red-brown powder dissolving in sulfuric acid to anolive-green solution having a yellow-red fluorescence and dyeing cottonfrom a grey-blue hydrosulfite vat fast Bordeaux-red tints.

6. The halogenated highly condensed heterocyclically bound anthraquinonederivative containing nitrogen which corresponds to the formula.

which product is a brown powder dissolving in sulfuric acid to a pureblue solution having a yellow-red fluorescence and dyeing cotton from ablue-black hydrosulfite vat fast yellow-brown tints.

WILHELM MOSER. WALTER. FIORONI.

